Carbodiimide-promoted epoxidation of olefins

Abstract

A method is provided for oxidizing an olefin to an epoxide by treating the olefin with hydrogen peroxide and a carbodiimide in the presence of an acid or base in a solvent system comprising a protic solvent. More specifically, a method is provided for oxidizing an olefin to an epoxide by contacting the olefin with aqueous hydrogen peroxide and a carbodiimide in the presence of a mild acid or mild base in a solvent system comprising a protic solvent.

What is claimed is: 
     
       1. A method for transferring an oxygen atom to an olefin comprising the step of: combining an olefin, hydrogen peroxide, a carbodiimide, and a reagent selected from the group of mild acid or mild base in a protic solvent system. 
     
     
       2. A method according to claim 1, wherein said carbodiimide is dicyclohexylcarbodiimide, N,N'-diisopropylcarbodiimide, or 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide. 
     
     
       3. A method according to claim 1, wherein said protic solvent system comprises methanol, ethanol, n-propanol or isopropyl alcohol. 
     
     
       4. A method according to claim 1, wherein said hydrogen peroxide is aqueous, containing about 1% to 99% water by volume. 
     
     
       5. A method according to claim 1, wherein said hydrogen peroxide is aqueous, containing about 2% to 97% water by volume. 
     
     
       6. A method according to claim 1, wherein said hydrogen peroxide is aqueous, containing about 50% to 90% water by volume. 
     
     
       7. A method according to claim 1, wherein said reagent is mild acid. 
     
     
       8. A method according to claim 1, wherein one mole equivalent of olefin substrate is reacted with more than one mole equivalent of carbodiimide; more than one mole equivalent of hydrogen peroxide; and mild acid. 
     
     
       9. A method according to claim 8, wherein the solvent system is methanol. 
     
     
       10. A method according to claim 1, wherein one mole equivalent of carbodiimide is reacted with more than one mole equivalent of olefin substrate; more than one mole equivalent of hydrogen peroxide; and mild acid. 
     
     
       11. A method according to claim 10, wherein the solvent system is ethanol. 
     
     
       12. A method according to claim 1 further comprising the step of heating said combination. 
     
     
       13. A method according to claim 1, wherein the product of the reaction is an epoxide. 
     
     
       14. A method for transferring an oxygen atom to an olefin comprising the step of: combining an olefin, hydrogen peroxide, a carbodiimide, and a mild cationic exchange resin in a protic solvent system. 
     
     
       15. A method for transferring an oxygen atom to an olefin which is not a fused aromatic olefin comprising the step of: combining an olefin, hydrogen peroxide, a carbodiimide, and a reagent selected from the group of mild acid or mild base in a protic solvent system. 
     
     
       16. The method of claim 15 wherein said protic solvent system is a substantially protic solvent system. 
     
     
       17. A method for transferring an oxygen atom to an olefin comprising the step of: combining an olefin, hydrogen peroxide, a carbodiimide, and a mild base in a protic solvent system.   
     
     
       18. A method according to claim 17, wherein said carbodiimide is dicyclohexylcarbodiimide, N,N'-diisopropylcarbodiimide, or 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide. 
     
     
       19. A method according to claim 17, wherein said protic solvent system comprises methanol, ethanol, n-propanol or isopropyl alcohol. 
     
     
       20. A method according to claim 17, wherein said hydrogen peroxide is aqueous, containing about 1% to 99% water by volume. 
     
     
       21. A method according to claim 17, wherein said hydrogen peroxide is aqueous, containing about 2% to 97% water by volume. 
     
     
       22. A method according to claim 17, wherein said hydrogen peroxide is aqueous, containing about 50% to 90% water by volume. 
     
     
       23. A method according to claim 17, wherein said reagent is selected from the group consisting of sodium bicarbonate, potassium bicarbonate, disodium hydrogen phosphate, or trisodium phosphate. 
     
     
       24. A method according to claim 17, wherein one mole equivalent of olefin substrate is combined with more than one mole equivalent of carbodiimide; more than one mole equivalent of mild base; and more than one mole equivalent of hydrogen peroxide. 
     
     
       25. A method according to claim 24, wherein the solvent system is methanol. 
     
     
       26. A method according to claim 17, wherein one mole equivalent of carbodiimide is combined with more than one mole equivalent of olefin substrate; one mole equivalent of mild base; and more than one mole equivalent of hydrogen peroxide. 
     
     
       27. A method according to claim 24, wherein the solvent system is ethanol. 
     
     
       28. A method according to claim 17 further comprising the step of heating said combination. 
     
     
       29. A method according to claim 17, wherein the product of the reaction is an epoxide.